高熵合金粉体制备及应用研究进展

doi:10.12034/j.issn.1009-606X.218259

摘要/Abstract

摘要： 高熵合金是近几年发展起来的新型合金，由于其优异的性能，如高延展性、高强度、优异的耐磨性、优异的耐蚀性和优异的高温稳定性，已成为热点材料之一。高熵合金粉体作为制备块体、涂层、薄膜材料及其它功能材料的原料，有着广阔的应用前景，但目前对高熵合金粉体尤其是高熵合金纳米粉体的研究较少。本工作根据当前高熵合金的研究进展，对高熵合金相形成的判据进行了划分，主要包括混合熵判据、混合焓判据、Ω判据和Hume?Rothery固溶理论判据。通过对各判据的总结，阐述了高熵合金固溶体相的形成规律，综述了高熵合金超细粉体和纳米粉体的制备方法，主要包括机械合金化法、气/水雾化法、化学还原法、碳热震荡法、等离子电弧放电法和扫描探针光刻技术，分析比较了不同方法的优缺点和应用前景，指出了高熵合金领域当前存在的问题和相应的解决方法，并对未来的发展作了展望。

关键词: 高熵合金, 固溶体判据, 高熵合金金粉体, 制备方法, 应用前景

Abstract: As a kind of new alloys, high entropy alloys have become one of the hotspot materials due to their outstanding remarkable physicochemical performances such as high ductility and strength, excellent wear resistance, outstanding corrosion resistance, and superior high temperature stability in recent years. Among these, high-entropy-alloy (HEA) powders have a much wider application, which not only can be used as raw material in the preparing of HEAs bulk, coatings and thin film materials, but also used as functional materials. However, there are few studies on HEA powders, especially on HEA nanoparticles. In this work, according to the current research progress of HEAs, the criterions for solid solution phase formation in HEAs were classified, which mainly include mixed entropy criterion, mixed enthalpy criterion, Ω criterion and Hume?Rothery solid solution theory criterion. Through the summary of each criterion, the solid-solution phase formation rules were also summarized. It provided a theoretical basis for more accurate prediction of the formation law of high entropy alloy solid solution phase and the design of new HEAs. Moreover, the preparation methods for HEA powders were reviewed. The HEA ultrafine powders were produced by mechanical alloying method and gas/water atomization method, and also the preparation methods of the HEA nanoparticles include chemical reduction method, carbothermal shock method, plasma arc discharge method and scanning probe lithography. In addition, the advantages and disadvantages of each method were also discussed, and these offered a wide range of flexible approaches for different type of applications of HEA powders. At the same time, current problems in the field of HEA powders research were pointed out, and the future developments were also prospected. This review had certain guiding significance for the expansion of the application of HEA powder subjects in the future direction.

Key words: high entropy alloys, solid solution criterion, high-entropy- alloy powders, preparation method, application prospects

权峰项厚政杨磊吴其辉冒爱琴俞海云. 高熵合金粉体制备及应用研究进展[J]. 过程工程学报, 2019, 19(3): 447-455.

Feng QUAN Houzheng XIANG Lei YANG Qihui WU Aiqin MAO Haiyun YU. Research progress in preparation and application of high-entropy-alloy powders[J]. Chin. J. Process Eng., 2019, 19(3): 447-455.

参考文献

[1] Yeh J W, Chen S K, Lin S J, et al.Nanostructured High-Entropy Alloys with Multiple Principal Elements: Novel Alloy Design Concepts and Outcomes[J]. Adv. Eng. Mater., 2004, 6 (5), 299-303. [2] Zhang Y, Zuo T T, Tang Z, et al.Microstructures and properties of high-entropy alloys[J]. Prog. Mater Sci., 2014, 61, 1-93. [3] Yeh J W, Chen Y L, Lin S J, et al.High-Entropy Alloys – A New Era of Exploitation[J]. Mater. Sci. Forum, 2007, 560, 1-9. [4] Tsai M H, Yeh J W.High-Entropy Alloys: A Critical Review[J]. Mater. Res. Lett., 2014, 2 (3), 107-123. [5] Lu Y, Gao X, Dong Y, et al.Preparing bulk ultrafine-microstructure high-entropy alloys via direct solidification[J]. Nanoscale, 2018, 10 (4), 1912-1919. [6] Joo S H, Kato H, Jang M J, et al.Structure and properties of ultrafine-grained CoCrFeMnNi high-entropy alloys produced by mechanical alloying and spark plasma sintering[J]. J. Alloys Compd., 2017, 698, 591-604. [7] Shang C, Axinte E, Sun J, et al.CoCrFeNi(W1 ? xMox) high-entropy alloy coatings with excellent mechanical properties and corrosion resistance prepared by mechanical alloying and hot pressing sintering[J]. Mater. Des., 2017, 117, 193-202. [8] He Y, Zhang J, Zhang H, et al.Effects of Different Levels of Boron on Microstructure and Hardness of CoCrFeNiAlxCu0.7Si0.1By High-Entropy Alloy Coatings by Laser Cladding[J]. Coatings, 2017, 7 (1). [9] Braeckman B R, Boydens F, Hidalgo H, et al.High entropy alloy thin films deposited by magnetron sputtering of powder targets[J]. Thin Solid Films, 2015, 580, 71-76. [10] He J Y, Wang H, Huang H L, et al.A precipitation-hardened high-entropy alloy with outstanding tensile properties[J]. Acta Materialia, 2016, 102, 187-196. [11] Liu B, Wang J, Chen J, et al.Ultra-High Strength TiC/Refractory High-Entropy-Alloy Composite Prepared by Powder Metallurgy[J]. Jom, 2017, 69 (4), 651-656. [12] 张勇, 非晶和高熵合金, 科学出版社, 2010. [13]Zhang Y, Amorphous and High Entropy Alloys, Science Press, 2010. [14] Otto F, Yang Y, Bei H, et al.Relative effects of enthalpy and entropy on the phase stability of equiatomic high-entropy alloys[J]. Acta Mater., 2013, 61 (7), 2628-2638. [15] 张勇, 陈明彪, 杨潇, 等.先进高熵合金技术[J]. 化工出版社, 2018. [16]Zhang Y, Chen M X, Yang W, et al.Advanced High Entropy Alloy Technology[J]. Chemical Industry Press, 2018. [17] Yang X, Zhang Y.Prediction of high-entropy stabilized solid-solution in multi-component alloys[J]. Mater. Chem. Phys., 2012, 132 (2), 233-238. [18] Wang Z, Huang Y, Yang Y, et al.Atomic-size effect and solid solubility of multicomponent alloys[J]. Scripta Mater., 2015, 94, 28-31. [19] Zhang Y, Lu Z P, Ma S G, et al.Guidelines in predicting phase formation of high-entropy alloys[J]. MRS Communications, 2014, 4 (2), 57-62. [20] Zhang Y, Zhou Y J, Lin J P, et al.Solid-Solution Phase Formation Rules for Multi-component Alloys[J]. Adv. Eng. Mater., 2008, 10 (6), 534-538. [21] Fang S, Xiao X, Xia L, et al.Relationship between the widths of supercooled liquid regions and bond parameters of Mg-based bulk metallic glasses[J]. J. Non-Cryst. Solids, 2003, 321 (1), 120-125. [22] Guo S, Ng C, Lu J, et al.Effect of valence electron concentration on stability of fcc or bcc phase in high entropy alloys[J]. J. Appl. Phys., 2011, 109 (10), 103505. [23] Tsai M H, Tsai K Y, Tsai C W, et al.Criterion for Sigma Phase Formation in Cr- and V-Containing High-Entropy Alloys[J]. Mater. Res. Lett., 2013, 1 (4), 207-212. [24] Guo S, Liu C T.Phase stability in high entropy alloys: Formation of solid-solution phase or amorphous phase[J]. Progress in Natural Science: Materials International, 2011, 21 (6), 433-446. [25] 蒋丽, CoFeNiV(Mo, Nb)高熵合金的组织演变及力学性能研究, 大连理工大学博士学位论文, 2016. [26]Jiang L， Research on the microstructure evolution and mechanical properties of CoFeNiV (Mo, Nb) high-entropy alloy, in, PhD thesis of Dalian University of Technology, 2016. [27] Salishchev G A, Tikhonovsky M A, Shaysultanov D G, et al.Effect of Mn and V on structure and mechanical properties of high-entropy alloys based on CoCrFeNi system[J]. J. Alloys Compd., 2014, 591, 11-21. [28] 龙卧云.机械合金化制备Zr-Al-Ni-Cu-Y非晶合金粉末及其低压烧结工艺探索[J]. 中南大学博士学位论文, 2012. [29]Long W Y.Preparation of Zr-Al-Ni-Cu-Y Amorphous Alloy Powder by Mechanical Alloying and Its Low Pressure Sintering Process[J]. Zhongnan University PhD thesis, 2012. [30] Yu P F, Zhang L J, Cheng H, et al.The high-entropy alloys with high hardness and soft magnetic property prepared by mechanical alloying and high-pressure sintering[J]. Intermetallics, 2016, 70, 82-87. [31] Ji W, Fu Z, Wang W, et al.Mechanical alloying synthesis and spark plasma sintering consolidation of CoCrFeNiAl high-entropy alloy[J]. J. Alloys Compd., 2014, 589, 61-66. [32] Mohanty S, Maity T N, Mukhopadhyay S, et al.Powder metallurgical processing of equiatomic AlCoCrFeNi high entropy alloy: Microstructure and mechanical properties[J]. Mater. Sci. Eng., A, 2017, 679, 299-313. [33] Varalakshmi S, Kamaraj M, Murty B S.Processing and properties of nanocrystalline CuNiCoZnAlTi high entropy alloys by mechanical alloying[J]. Mater. Sci. Eng., A, 2010, 527 (4), 1027-1030. [34] Varalakshmi S, Kamaraj M, Murty B S.Synthesis and characterization of nanocrystalline AlFeTiCrZnCu high entropy solid solution by mechanical alloying[J]. J. Alloys Compd., 2008, 460 (1), 253-257. [35] Maulik O, Kumar D, Kumar S, et al.Structural evolution of spark plasma sintered AlFeCuCrMgx (x = 0, 0.5, 1, 1.7) high entropy alloys[J]. Intermetallics, 2016, 77, 46-56. [36] Praveen S, Murty B S, Kottada R S.Alloying behavior in multi-component AlCoCrCuFe and NiCoCrCuFe high entropy alloys[J]. Mater. Sci. Eng., A, 2012, 534, 83-89. [37] 陈永星, 朱胜, 王晓明, 等.AlFeCrCoNi高熵合金的机械合金化法制备及退火行为研究[J]. 西安工业大学学报, 2015, 2, 162-166. [38]Chen Y X, Zhu S, Wang X M, et al.Preparation and Annealing Behavior of AlFeCrCoNi High-Entropy Alloy by Mechanical Alloying[J]. Journal of Xi' an Technological University, 2015, 2, 162-166. [39] Raphel A, Kumaran S, Kumar K V, et al.Oxidation and Corrosion resistance of AlCoCrFeTiHigh Entropy Alloy[J]. Materials Today: Proceedings, 2017, 4 (2, Part A), 195-202. [40] Kumar D, Maulik O, Kumar S, et al.Phase and thermal study of equiatomic AlCuCrFeMnW high entropy alloy processed via spark plasma sintering[J]. Mater. Chem. Phys., 2018, 210, 71-77. [41] Ding P, Mao A, Zhang X, et al.Preparation, characterization and properties of multicomponent AlCoCrFeNi2.1 powder by gas atomization method[J]. J. Alloys Compd., 2017, 721, 609-614. [42] Yang C C, Hang Chau J L, Weng C J, et al.Preparation of high-entropy AlCoCrCuFeNiSi alloy powders by gas atomization process[J]. Mater. Chem. Phys., 2017, 202, 151-158. [43] Ei?mann N, Kl?den B, Wei?g?rber T, et al.High-entropy alloy CoCrFeMnNi produced by powder metallurgy[J]. Powder Metall., 2017, 60 (3), 184-197. [44] Yim D, Jang M J, Bae J W, et al.Compaction behavior of water-atomized CoCrFeMnNi high-entropy alloy powders[J]. Mater. Chem. Phys., 2018, 210, 95-102. [45] 董阳阳.真空雾化制备CoCrAlTaY 高温合金粉末及其涂层抗氧化性能[J]. 昆明理工大学硕士学位论文, 2015. [46]Dong Y Y.Preparation of CoCrAlTaY Superalloy Powder by Vacuum Atomization and Its Antioxidant Properties[J]. Kunming University of Science and Technology, Master' s Thesis, 2015. [47] 陈美英, 胡敦元, 孙建刚, 等.真空雾化法制备MCrAlTaY 合金粉末[J]. 热喷涂技术, 2010, (1), 27-29. [48]Chen M Y, Hu D Y, Sun J G, et al.Preparation of MCrAlTaY alloy powder by vacuum atomization method[J]. Thermal Spray Technology, 2010, (1), 27-29. [49] Chen P C, Liu G, Zhou Y, et al.Tip-Directed Synthesis of Multimetallic Nanoparticles[J]. J. Am. Chem. Soc., 2015, 137 (28), 9167-9173. [50] Chen C, Kang Y, Huo Z, et al.Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces[J]. Science, 2014, 343 (6177), 1339-1343. [51] Gordon T R, Schaak R E.Synthesis of Hybrid Au-In2O3 Nanoparticles Exhibiting Dual Plasmonic Resonance[J]. Chem. Mater., 2014, 26 (20), 5900-5904. [52] Linic S, Aslam U, Boerigter C, et al.Photochemical transformations on plasmonic metal nanoparticles[J]. Nature Materials, 2015, 14, 567. [53] N.S A, Eugenii K, Itamar W. Nanoparticle Arrays on Surfaces for Electronic, Optical, and Sensor Applications[J]. ChemPhysChem, 2000, 1 (1), 18-52. [54] Mohan P, Takahashi M, Higashimine K, et al.AuFePt Ternary Homogeneous Alloy Nanoparticles with Magnetic and Plasmonic Properties[J]. Langmuir, 2017, 33 (7), 1687-1694. [55] Aslam U, Chavez S, Linic S.Controlling energy flow in multimetallic nanostructures for plasmonic catalysis[J]. Nature Nanotechnology, 2017, 12, 1000. [56] Zhong C J, Luo J, Njoki P N, et al.Fuel cell technology: nano-engineered multimetallic catalysts[J]. Energy & Environmental Science, 2008, 1 (4), 454-466. [57] Bogdanov A A, Dixon A J, Gupta S, et al.Synthesis and Testing of Modular Dual-Modality Nanoparticles for Magnetic Resonance and Multispectral Photoacoustic Imaging[J]. Bioconjugate Chem., 2016, 27 (2), 383-390. [58] Ferrando R, Jellinek J, Johnston R L.Nanoalloys:? From Theory to Applications of Alloy Clusters and Nanoparticles[J]. Chem. Rev., 2008, 108 (3), 845-910. [59] Singh M P, Srivastava C.Synthesis and electron microscopy of high entropy alloy nanoparticles[J]. Mater. Lett., 2015, 160, 419-422. [60] Ortiz N, Weiner R G, Skrabalak S E.Ligand-Controlled Co-reduction versus Electroless Co-deposition: Synthesis of Nanodendrites with Spatially Defined Bimetallic Distributions[J]. ACS Nano, 2014, 8 (12), 12461-12467. [61] 王国涛.高温合金纳米粒子电弧法制备及光谱特征[J]. 大连理工大学硕士学位论文, 2015. [62]Wang G T.Preparation and Spectral Characteristics of High Temperature Alloy Nanoparticle Arc Method[J]. Master thesis of Dalian University of Technology, 2015. [63] Safari A, Gheisari K, Farbod M.Characterization of Ni ferrites powders prepared by plasma arc discharge process[J]. J. Magn. Magn. Mater., 2017, 421, 44-51. [64] Mohammadian A R, Hajarpour S, Gheisari K, et al.Synthesis of Ni–Mn ferrite–chromite nanoparticles through plasma arc discharge[J]. Mater. Lett., 2014, 133, 91-93. [65] Karbalaei Akbari M, Derakhshan R, Mirzaee O.A case study in vapor phase synthesis of Mg–Al alloy nanoparticles by plasma arc evaporation technique[J]. Chem. Eng. J., 2015, 259, 918-926. [66] Geng D Y, Park W Y, Kim J C, et al.Synthesis and Characterization of FeCoNiAl Nanocapsules by Plasma arc Discharge Process[J]. J. Mater. Res., 2011, 20 (09), 2534-2543. [67] Mao A, Ding P, Quan F, et al.Effect of aluminum element on microstructure evolution and properties of multicomponent Al-Co-Cr-Cu-Fe-Ni nanoparticles[J]. J. Alloys Compd., 2018, 735, 1167-1175. [68] Chen P C, Liu X, Hedrick J L, et al.Polyelemental nanoparticle libraries[J]. Science, 2016, 352 (6293), 1565-1569.